@article {49044,
	title = {Role of aromatic alcohol additives on asymmetric organocatalysis reactions: insights from theory},
	journal = {Chemistry-an asian jounrnal},
	volume = {19},
	year = {2024},
	month = {FEB },
	type = {Article},
	abstract = {<p>
	The presence of an aromatic additive has been seen to enhance, often significantly, the enantioselectivity and yield in asymmetric organocatalysis. Considering their success across a dizzying range of organocatalysts and organic transformations, it would seem unlikely that a common principle exists for their functioning. However, the current investigations with DFT suggest a general principle: the phenolic additive sandwiches itself, through hydrogen bonding and pi \&amp; sdot;\&amp; sdot;\&amp; sdot;pi stacking, between the organocatalyst coordinated electrophile and nucleophile. This is seen for a wide range of experimentally reported systems. That such complex formation leads to enhanced stereoselectivity is then demonstrated for two cases: the cinchona alkaloid complex (BzCPD), catalysing thiocyanation (2-naphthol additive employed), as well as for L-pipecolicacid catalysing the asymmetric nitroaldol reaction with a range of nitro-substituted phenol additives. These findings, indicating that dual catalysis takes place when phenolic additives are employed, are likely to have a significant impact on the field of asymmetric organocatalysis. The current DFT based study, on a wide range of organocatalysis systems, reveals a general principle by which phenolic additives influence asymmetric organocatalysis reactions. It is shown that the phenolic additive forms a sandwich complex, through hydrogen bonding and pi \&amp; sdot;\&amp; sdot;\&amp; sdot;pi stacking interactions, with the organocatalyst coordinated electrophile and nucleophile, and enhances the enantioselectivity of the system as a result. image</p>
},
	keywords = {Additive, Asymmetric Organocatalysis, Cinchona Alkaloid, Density functional theory, Enantioselective Thiocyanation},
	issn = {1861-4728},
	doi = {10.1002/asia.202300997},
	author = {Banerjee, Subhrashis and Vanka, Kumar}
}
